JP6237150B2 - Conductive composition - Google Patents
Conductive composition Download PDFInfo
- Publication number
- JP6237150B2 JP6237150B2 JP2013240682A JP2013240682A JP6237150B2 JP 6237150 B2 JP6237150 B2 JP 6237150B2 JP 2013240682 A JP2013240682 A JP 2013240682A JP 2013240682 A JP2013240682 A JP 2013240682A JP 6237150 B2 JP6237150 B2 JP 6237150B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- copper
- methyl
- conductive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Conductive Materials (AREA)
Description
本発明は、導電性組成物に関し、更に詳細には、導電性及び保存安定性に優れ、印刷回路用途に極めて有用な導電性組成物に関する。 The present invention relates to a conductive composition, and more particularly to a conductive composition that is excellent in conductivity and storage stability and is extremely useful for printed circuit applications.
近年、プリンテッドエレクトロニクスへの注目が高まっており、回路、コンデンサ素子、半導体素子等を構成する電極・配線や強誘電体材料、半導体材料等をスクリーン印刷やグラビア印刷といった印刷手法にて配置する試みがなされている。中でも電極・配線の形成においては、金属粉を主成分とする印刷回路用導電性組成物が広く用いられている。
このような導電性組成物においては、金属粉の１次粒子が凝集することで、粗大な２次粒子を形成しやすく、その結果、導電性組成物の安定性や導電性が低下することが知られている。こうした金属粉の凝集に対して、凝集を防ぐ分散剤を導電性組成物中に添加することが提案されている。該分散剤としては例えばラウロイルサルコシン（Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸）等のサルコシン化合物およびその金属塩が有効であり、特許文献１及び２には、分散剤としてこれらを含有する導電性組成物が提案されている。
例えば、特許文献２の導電性組成物は金属粉の凝集が抑制されているので、該導電性組成物より得られる塗膜の体積抵抗率は１０-3Ω・ｃｍ以下と導電性に優れている。しかし、特許文献２の発明では、導電性組成物の経時的な粘度変化や経時的な導電性の低下が起こり、保存安定性に劣るという問題がある。印刷手法においては、導電性組成物の粘度と印刷性には密接な相関があることから、導電性組成物を安定して印刷する上で、導電性組成物の粘度変化は好ましくない。
In recent years, attention has been focused on printed electronics, and attempts have been made to place electrodes, wiring, ferroelectric materials, semiconductor materials, etc. that constitute circuits, capacitor elements, semiconductor elements, etc. by printing methods such as screen printing and gravure printing. Has been made. In particular, in the formation of electrodes / wirings, printed circuit conductive compositions containing metal powder as a main component are widely used.
In such a conductive composition, the primary particles of the metal powder aggregate to easily form coarse secondary particles, and as a result, the stability and conductivity of the conductive composition may decrease. Are known. For such agglomeration of the metal powder, it has been proposed to add a dispersant for preventing the aggregation to the conductive composition. As the dispersant, for example, sarcosine compounds such as lauroyl sarcosine (N-methyl-N-dodecanoylaminoacetic acid) and metal salts thereof are effective. Patent Documents 1 and 2 include conductive materials containing these as dispersants. Compositions have been proposed.
For example, since the conductive composition of Patent Document 2 suppresses the aggregation of metal powder, the volume resistivity of the coating film obtained from the conductive composition is 10 −3 Ω · cm or less and has excellent conductivity. Yes. However, in the invention of Patent Document 2, there is a problem that the viscosity of the conductive composition changes with time and the conductivity decreases with time, resulting in poor storage stability. In the printing method, since there is a close correlation between the viscosity of the conductive composition and the printability, a change in the viscosity of the conductive composition is not preferable in stably printing the conductive composition.
上記経時的な粘度変化や導電性の低下は、使用される分散剤の酸としての作用に起因するものと考えられている。すなわち、粘度変化は、該導電性組成物に含有される樹脂と酸との反応により発生し、導電性の低下は、酸により金属粒子表面での酸化が促進され、酸化膜が急速に増加することで発生すると考えられている。
特許文献３では、導電性組成物の酸性度を低下させるために、無機塩基やアミン化合物等の塩基性化合物を添加する技術が開示され、特許文献４及び５では、分散剤を金属塩とする技術が開示されている。また、特許文献６では、防錆剤を添加して酸化を抑制する技術が開示されている。
It is considered that the above-described change in viscosity and decrease in conductivity are caused by the action of the dispersant used as an acid. That is, a change in viscosity is caused by a reaction between the resin contained in the conductive composition and an acid, and a decrease in conductivity is promoted by oxidation on the metal particle surface by the acid, and the oxide film rapidly increases. It is thought that it occurs by.
Patent Document 3 discloses a technique of adding a basic compound such as an inorganic base or an amine compound in order to reduce the acidity of the conductive composition. Patent Documents 4 and 5 disclose a metal salt as a dispersant. Technology is disclosed. Moreover, in patent document 6, the technique which suppresses oxidation by adding a rust preventive agent is disclosed.
特許文献３〜５に開示の技術では、導電性組成物の酸性度を低下させることによって、粘度変化防止及び酸化が抑制されることによる導電性の低下防止ができるものの、自然酸化自体を抑制することはできない。また、特許文献６に開示の技術において、防錆剤の作用機構は、金属表面に強固な保護層を形成して酸との反応を防止する点にあるが、該保護層の導電性が低いために導電性組成物の導電性が低下するという問題がある。
そこで本発明の課題は、酸化抑制効果が高く、また導電性組成物の導電性を低下させることなく、さらに粘度及び導電性の経時的変化が小さく、かつ安定した印刷特性を有する、金属粉末含有の導電性組成物を提供することにある。
In the techniques disclosed in Patent Documents 3 to 5, by reducing the acidity of the conductive composition, it is possible to prevent viscosity change and to prevent decrease in conductivity due to suppression of oxidation, but suppress natural oxidation itself. It is not possible. In the technique disclosed in Patent Document 6, the mechanism of action of the rust inhibitor is to form a strong protective layer on the metal surface to prevent reaction with acid, but the conductivity of the protective layer is low. Therefore, there exists a problem that the electroconductivity of an electroconductive composition falls.
Accordingly, an object of the present invention is to contain a metal powder that has a high oxidation-inhibiting effect, does not lower the conductivity of the conductive composition, has a small change in viscosity and conductivity over time, and has stable printing characteristics. It is providing the conductive composition of this.
本発明によれば、（ａ）金属粉末、（ｂ）樹脂及び（ｃ）式（１）で表される化合物を含み、必要に応じて（ｄ）アミンを含有してなり、（ａ）金属粉末の元素と（ｃ）式（１）で表される化合物を構成する金属Ｍの元素が同一である導電性組成物が提供される。
本発明の導電性組成物は、（ｃ）式（１）で表される化合物が金属塩であるために、該導電性組成物の酸性度が低くなり、粘度の経時変化を抑制することができる。更に（ａ）金属粉末を構成する金属元素と、（ｃ）式（１）で表される化合物を構成する金属元素Ｍが同一であるために、導電性組成物中にて、（ａ）金属粉末および（ｃ）式（１）で表される化合物を構成する金属元素の金属イオン濃度が増加することで、金属と金属イオン間の平衡が金属側に偏り、金属の酸化を抑制することができる。また、上記の導電性組成物は、更には必要に応じて（ｄ）アミンを含有するため、初期の導電性に優れ、さらに経時後の粘度及び抵抗率について初期値からの変化が小さく、保存安定性に優れる。従って、本発明の導電性組成物を用いて、例えば、スクリーン印刷、グラビア印刷等の印刷手法にて印刷回路を作製する際に、導電性組成物の保存安定性と印刷回路の導電性を両立することができる。 In the conductive composition of the present invention, (c) the compound represented by the formula (1) is a metal salt, so that the acidity of the conductive composition is reduced and the change in viscosity over time is suppressed. it can. Furthermore, since (a) the metal element constituting the metal powder and (c) the metal element M constituting the compound represented by the formula (1) are the same, (a) the metal in the conductive composition By increasing the metal ion concentration of the metal element constituting the powder and the compound represented by (c) formula (1), the equilibrium between the metal and the metal ion is biased toward the metal side, and the metal oxidation is suppressed. it can. In addition, the conductive composition further contains (d) an amine as necessary, so that the initial conductivity is excellent, and the viscosity and resistivity after time are small from the initial value and stored. Excellent stability. Therefore, using the conductive composition of the present invention, for example, when producing a printed circuit by a printing technique such as screen printing or gravure printing, the storage stability of the conductive composition and the conductivity of the printed circuit are compatible. can do.
本発明に用いる（ａ）金属粉末（以下、（ａ）成分ということがある）は、金属の粉末であれば特に限定されないが、例えば、金属種としては、銅、ニッケル、コバルト、亜鉛、鉄、アルミニウム、パラジウム、白金、スズ、銀、又は金等が挙げられる。なお、（ｃ）の金属元素も対応する複合金属塩とすることにより、上記これらを含む合金も使用し得る。特に、銅粉が導電性および汎用性の面から好ましい。また、金属粒子の作製方法は、電解法、湿式還元法等の湿式法、アトマイズ法、粉砕物等を好ましく挙げることができる。該金属粉末の粒径は、保存安定性の点で、０．０１〜１００μｍ、特に０．０５〜３０μｍの範囲であるのが好ましい。 The (a) metal powder used in the present invention (hereinafter sometimes referred to as the component (a)) is not particularly limited as long as it is a metal powder, but examples of the metal species include copper, nickel, cobalt, zinc, and iron. , Aluminum, palladium, platinum, tin, silver, or gold. In addition, the alloy containing these can also be used by making the metal element of (c) into the corresponding composite metal salt. In particular, copper powder is preferable from the viewpoints of conductivity and versatility. As a method for producing the metal particles, a wet method such as an electrolytic method or a wet reduction method, an atomizing method, a pulverized product, or the like can be preferably exemplified. The particle size of the metal powder is preferably in the range of 0.01 to 100 μm, particularly 0.05 to 30 μm from the viewpoint of storage stability.
本発明の導電性組成物に用いる（ｂ）樹脂（以下、（ｂ）成分ということがある）は特に限定されるものではなく、導電性組成物に用いられる公知の樹脂（熱硬化性樹脂、熱可塑性樹脂、光硬化性樹脂等。）を好ましく挙げることができる。例えば、熱可塑性樹脂としては、ポリエステル、ポリエチレン、ポリオレフィン、ポリカーボネート、アミド樹脂、イミド樹脂、シリコン樹脂、フッ素樹脂、等が、熱硬化性樹脂としてはアクリレート樹脂、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、オキサジン樹脂、オキセタン樹脂、キシレン樹脂、グアナミン樹脂、ジアリルフタレート樹脂、シリコン樹脂、ビスマレイドトリアジン樹脂、ビニルエステル樹脂、フェノール樹脂、フラン樹脂、メラミン樹脂、不飽和ポリエステル、尿素樹脂、等を好ましく挙げることができ、使用に際しては単独又は複数の樹脂を併用して用いることができる。また、これらの樹脂は硬化剤、硬化触媒等と併用して用いても良い。特に、熱硬化性樹脂を用いた場合、重合時の体積収縮が大きいことで導電性組成物中の金属粒子同士が強く接触することになり、導電性が高くなるため好ましい。 The (b) resin used in the conductive composition of the present invention (hereinafter sometimes referred to as the component (b)) is not particularly limited, and a known resin (thermosetting resin, Preferred examples include thermoplastic resins and photocurable resins. For example, polyester, polyethylene, polyolefin, polycarbonate, amide resin, imide resin, silicon resin, fluorine resin, etc. are used as the thermoplastic resin, and acrylate resin, acrylic resin, urethane resin, epoxy resin, oxazine are used as the thermosetting resin. Preferred examples include resins, oxetane resins, xylene resins, guanamine resins, diallyl phthalate resins, silicone resins, bismaleidotriazine resins, vinyl ester resins, phenol resins, furan resins, melamine resins, unsaturated polyesters, urea resins, and the like. In use, a single resin or a plurality of resins can be used in combination. These resins may be used in combination with a curing agent, a curing catalyst, and the like. In particular, when a thermosetting resin is used, the volumetric shrinkage at the time of polymerization is large, so that the metal particles in the conductive composition come into strong contact with each other, and the conductivity becomes high.
本発明において、前記（ａ）成分と、（ｂ）成分との配合割合は、これらの合計量を１００重量部とした場合、好ましくは（ａ）成分５０〜９８重量部、特に好ましくは６５〜９３重量部、よって、好ましくは（ｂ）成分２〜５０重量部、特に好ましくは７〜３５重量部である。（ａ）成分と（ｂ）成分との配合割合が上記範囲外の場合には、樹脂の不足により銅粉同士が十分に接触しない点または樹脂による導通阻害が発生する点により、導電性が低下するおそれがある。 In the present invention, the blending ratio of the component (a) and the component (b) is preferably 50 to 98 parts by weight, particularly preferably 65 to 98 parts by weight when the total amount thereof is 100 parts by weight. 93 parts by weight, and therefore preferably 2 to 50 parts by weight of component (b), particularly preferably 7 to 35 parts by weight. When the blending ratio of the component (a) and the component (b) is outside the above range, the conductivity is lowered due to the point that the copper powder does not sufficiently contact with each other due to the lack of the resin or the point where the conduction is inhibited by the resin. There is a risk.
本発明に用いる（ｃ）式（１）で表される化合物（以下、（ｃ）成分ということがある）において、式（１）中Ｒ1及びＲ2はそれぞれ独立に、水素原子、ブチル基、デシル基、ドコシル基等の炭素数１〜２２のアルキル基、又はブテニル基、デセニル基、ドコセニル基等の炭素数２〜２２のアルケニル基を示す。Ｒ1としては、特に炭素数１０〜１８のアルキル基又は炭素数１０〜１８のアルケニル基を好ましく挙げられる。また、Ｒ2としては、特に炭素数１〜１０のアルキル基又は炭素数２〜１０のアルケニル基を好ましく挙げられる。
式（１）中ｎは１〜１０の整数、好ましくは１〜５の整数である。ｘは１〜４の整数であり、金属Ｍの価数を示す。Ｍは銅、ニッケル、コバルト、亜鉛、鉄、アルミニウム、パラジウム、白金、スズ、銀、又は金である。
In the compound (c) represented by formula (1) used in the present invention (hereinafter sometimes referred to as component (c)), R 1 and R 2 in formula (1) are each independently a hydrogen atom or a butyl group. , An alkyl group having 1 to 22 carbon atoms such as decyl group and docosyl group, or an alkenyl group having 2 to 22 carbon atoms such as butenyl group, decenyl group and dococenyl group. R 1 is particularly preferably an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms. R 2 is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
In formula (1), n is an integer of 1 to 10, preferably an integer of 1 to 5. x is an integer of 1 to 4 and represents the valence of the metal M. M is copper, nickel, cobalt, zinc, iron, aluminum, palladium, platinum, tin, silver, or gold.
（ｃ）成分としては、例えば、式（１）のＭが銅の場合、Ｎ−メチル−Ｎ−デカノイルアミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ9Ｈ19、Ｒ2がＣＨ3、ｎが１の化合物）、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ11Ｈ23、Ｒ2がＣＨ3、ｎが１の化合物）、Ｎ−メチル−Ｎ−テトラデカノイルアミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ13Ｈ27、Ｒ2がＣＨ3、ｎが１の化合物）、Ｎ−メチル−Ｎ−ヘキサデカノイルアミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ15Ｈ31、Ｒ2がＣＨ3、ｎが１の化合物）、Ｎ−メチル−Ｎ−オクタデカノイルアミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ17Ｈ35、Ｒ2がＣＨ3、ｎが１の化合物）、Ｎ−メチル−Ｎ−［（Ｚ）−１−オキソ−９−オクタデセニル］アミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ17Ｈ33、Ｒ2がＣＨ3、ｎが１の化合物）、Ｎ−メチル−Ｎ−ドコサノイルアミノ酢酸銅（ＩＩ）（式（１）中のＲ1がＣ21Ｈ43、Ｒ2がＣＨ3、ｎが１の化合物）等のＮ−メチル−Ｎ−アルカノイルアミノ酢酸銅；ヤシ油脂肪酸サルコシン銅、トール油抽出脂肪酸サルコシン銅等の混合脂肪酸サルコシン銅；３−［Ｎ−メチル−Ｎ−デカノイルアミノ］プロピオン酸銅（式（１）中のＲ1がＣ9Ｈ19、Ｒ2がＣＨ3、ｎが２の化合物）、３−［Ｎ−メチル−Ｎ−ドデカノイルアミノ］プロピオン酸銅（ＩＩ）（式（１）中のＲ1がＣ11Ｈ23、Ｒ2がＣＨ3、ｎが２の化合物）、３−［Ｎ−メチル−Ｎ−テトラデカノイルアミノ］プロピオン酸銅（ＩＩ）（式（１）中のＲ1がＣ13Ｈ27、Ｒ2がＣＨ3、ｎが２の化合物）、３−［Ｎ−メチル−Ｎ−ヘキサデカノイルアミノ］プロピオン酸銅（ＩＩ）（式（１）中のＲ1がＣ15Ｈ31、Ｒ2がＣＨ3、ｎが２の化合物）、３−［Ｎ−メチル−Ｎ−オクタデカノイルアミノ］プロピオン酸銅（ＩＩ）（式（１）中のＲ1がＣ17Ｈ35、Ｒ2がＣＨ3、ｎが２の化合物）、３−［Ｎ−メチル−Ｎ−ドコサノイルアミノ］プロピオン酸銅（ＩＩ）（式（１）中のＲ1がＣ21Ｈ43、Ｒ2がＣＨ3、ｎが２の化合物）を好ましく挙げることができる。
また、（ｃ）成分のＭとしては、銅以外に、ニッケル、コバルト、亜鉛、鉄、アルミニウム、パラジウム、白金、スズ、銀、又は金を用いることができる。
As the component (c), for example, when M in the formula (1) is copper, N-methyl-N-decanoylaminoacetate copper (II) (R 1 in the formula (1) is C 9 H 19 , R 2 is CH 3 , n is a compound of 1), N-methyl-N-dodecanoylaminoacetate copper (II) (wherein R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1 Compound), N-methyl-N-tetradecanoylaminoacetate copper (II) (compound in which R 1 is C 13 H 27 , R 2 is CH 3 and n is 1 in formula (1)), N-methyl -N-hexadecanoylamino copper acetate (II) (compound in which R 1 is C 15 H 31 , R 2 is CH 3 and n is 1 in formula (1)), N-methyl-N-octadecanoylamino Copper (II) acetate (a compound in which R 1 in formula (1) is C 17 H 35 , R 2 is CH 3 , and n is 1), N-methyl-N-[(Z) -1-oxo-9- Octadeseni ] Amino copper acetate (II) (wherein (1) R 1 is C 17 H 33, R 2 is CH 3, n is compound 1 in), N- methyl -N- docosanol alkanoylamino copper acetate (II) ( N-methyl-N-alkanoylaminoacetate copper such as R 1 is C 21 H 43 , R 2 is CH 3 and n is 1 in formula (1); palm oil fatty acid sarcosine copper, tall oil extracted fatty acid sarcosine Mixed fatty acid sarcosine copper such as copper; 3- [N-methyl-N-decanoylamino] propionic acid copper (R 1 in formula (1) is C 9 H 19 , R 2 is CH 3 , n is 2 compound ), 3- [N-methyl-N-dodecanoylamino] propionic acid copper (II) (compound in which R 1 is C 11 H 23 , R 2 is CH 3 and n is 2 in formula (1)), 3 - [N-methyl--N- tetradecanoyl amino] R 1 in copper propionate (II) (formula (1) is C 13 H 27, R 2 CH 3, n is 2 compounds), 3- R 1 is C 15 H 31 of [N- methyl -N- hexadecanoylamino] propionic copper (II) (formula (1), R 2 is CH 3 , N is a compound of 2), 3- [N-methyl-N-octadecanoylamino] propionic acid copper (II) (in formula (1), R 1 is C 17 H 35 , R 2 is CH 3 , n Is a compound of 2), 3- [N-methyl-N-docosanoylamino] propionic acid copper (II) (wherein R 1 in formula (1) is C 21 H 43 , R 2 is CH 3 , n is 2 Compound) can be mentioned preferably.
Moreover, as M of (c) component, nickel, cobalt, zinc, iron, aluminum, palladium, platinum, tin, silver, or gold other than copper can be used.
本発明において（ｃ）成分の配合割合は、前記（ａ）成分と（ｂ）成分との合計量１００重量部に対して、好ましくは０．５〜１５重量部、特に好ましくは１〜１０重量部である。（ｃ）成分の配合割合が前記０．５重量部未満の場合には、（ｃ）成分による酸化膜除去が十分でなく導電性が低下するおそれがあり、前記１５重量部を超える場合には、（ｃ）成分自体の導通阻害効果が大きくなり、導電性が低下するおそれがある。 In the present invention, the blending ratio of the component (c) is preferably 0.5 to 15 parts by weight, particularly preferably 1 to 10 parts by weight based on 100 parts by weight of the total amount of the component (a) and the component (b). Part. When the blending ratio of the component (c) is less than 0.5 parts by weight, there is a risk that the oxide film removal by the component (c) is not sufficient and the conductivity may be reduced. , (C) The continuity-inhibiting effect of the component itself is increased, and the conductivity may be reduced.
本発明の導電性組成物は、上記（ａ）〜（ｃ）成分以外に、本発明の効果を損なわない範囲で、または更に効果を改善する等の目的で、他の成分を含有させることができる。
他の成分としては、例えば、本発明の導電性組成物の導電性及び保存安定性を更に向上させる（ｄ）アミン（以下、（ｄ）成分ということがある）が挙げられ、該（ｄ）成分としては、例えば、脂肪族アミン、芳香族アミン等を挙げることができる。具体的には脂肪族アミンとして、例えば、ブチルアミン、アミルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、２−エチルヘキシルアミン、ジイソプロピルアミン、トリエチルアミン、テトラメチルエチレンジアミン、エチレンジアミン、プロピレンジアミン、ラウロイルプロピレンジアミン、パルミトイルプロピレンジアミン、ステアリルプロピレンジアミン、オレイルブロピレンジアミン等を挙げることができる。また芳香族アミンとしては、例えば、アニリン、ｏ−アミノフェノール、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４−（４−スルホベンジル）アミノアニリン、４−ジメチルアミノアニリン、４−ジエチルアミノアニリン、２−アミノ−５−ジエチルアミノトルエン、４−［Ｎ−（β−ヒドロキシエチル）アミノ］アニリン、４−［Ｎ，Ｎ−ジ−（β−ヒドロキシエチル）アミノ］アニリンを挙げることができる。
In addition to the components (a) to (c), the conductive composition of the present invention may contain other components for the purpose of further improving the effect within a range not impairing the effects of the present invention. it can.
Examples of the other component include (d) amine (hereinafter also referred to as (d) component) that further improves the conductivity and storage stability of the conductive composition of the present invention. Examples of the component include aliphatic amines and aromatic amines. Specifically, as the aliphatic amine, for example, butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, diisopropylamine, triethylamine, tetramethylethylenediamine, ethylenediamine, propylenediamine, lauroylpropylenediamine, palmitoylpropylenediamine , Stearylpropylenediamine, oleylbropyrenediamine and the like. Examples of the aromatic amine include aniline, o-aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4- (4-sulfobenzyl) aminoaniline, 4-dimethylaminoaniline, 4- Examples include diethylaminoaniline, 2-amino-5-diethylaminotoluene, 4- [N- (β-hydroxyethyl) amino] aniline, and 4- [N, N-di- (β-hydroxyethyl) amino] aniline. .
本発明において、（ｄ）成分を含有させる場合の配合割合は、前記（ｃ）成分１００重量部に対して、好ましくは１０〜１０００重量部、特に好ましくは２０〜５００重量部の範囲である。（ｄ）成分の配合割合が前記１０００重量部を超える場合には、（ｄ）成分自体の導通阻害効果が大きくなり、導電性が低下するおそれがある。 In the present invention, the blending ratio when component (d) is contained is preferably 10 to 1000 parts by weight, particularly preferably 20 to 500 parts by weight, per 100 parts by weight of component (c). When the blending ratio of the component (d) exceeds 1000 parts by weight, the conductivity inhibiting effect of the component (d) itself is increased, and the conductivity may be lowered.
本発明の導電性組成物を調製するには、例えば、上記（ａ）〜（ｃ）成分を、また必要に応じて（ｄ）アミン等の他の成分を混合し、混練することにより得ることができる。また導電性組成物を調製する際に、必要に応じてブチルカルビトール（２−（２−ブトキシエトキシ）エタノール）等の粘度調整剤、消泡剤、増粘剤、皮張り防止剤や、樹脂の硬化性に影響を与える反応性希釈剤、硬化触媒等の添加剤等を適宜添加することも可能である。 In order to prepare the conductive composition of the present invention, for example, the above components (a) to (c) are obtained by mixing and kneading other components such as (d) amine as necessary. Can do. Further, when preparing the conductive composition, a viscosity modifier such as butyl carbitol (2- (2-butoxyethoxy) ethanol), an antifoaming agent, a thickening agent, an anti-skinning agent, or a resin, if necessary. It is also possible to appropriately add additives such as a reactive diluent and a curing catalyst that affect the curability of the resin.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれらに限定されない。
まず、（ｃ）成分の合成例を以下に示す。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
First, a synthesis example of the component (c) is shown below.
合成例１：Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸８６重量部、エタノール７９３０重量部及び水１００重量部を混合し溶液を調製した。ここに、ヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末８７重量部を得た。この粉末の熱重量分析における加熱残分は１３．４％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノ酢酸銅（ＩＩ）無水物の計算結果である１３．２％とほぼ一致した。
Synthesis Example 1: N-methyl-N-dodecanoylaminoacetic acid copper (II) anhydride (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1, x is 2, M Was prepared by mixing 36 parts by weight of copper nitrate (II) trihydrate, 86 parts by weight of N-methyl-N-dodecanoylaminoacetic acid, 7930 parts by weight of ethanol and 100 parts by weight of water. . A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 87 parts by weight of a light blue powder. The heat residue of this powder in the thermogravimetric analysis was 13.4%, which almost coincided with the calculated result of 13.2% for N-methyl-N-dodecanoylamino copper acetate (II) anhydride.
合成例２：Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸ニッケル（ＩＩ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが２、Ｍがニッケルの化合物）の合成
硝酸ニッケル（ＩＩ）６水和物４４重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸８６重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、薄緑色粉末８８重量部を得た。この粉末の熱重量分析における加熱残分が１１．８％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノ酢酸ニッケル（ＩＩ）無水物の計算結果である１２．２％とほぼ一致した。
Synthesis Example 2: N-methyl-N-dodecanoylaminoacetic acid nickel (II) anhydride (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1, x is 2, M Is a nickel compound) A solution comprising 44 parts by weight of nickel (II) nitrate hexahydrate, 86 parts by weight of N-methyl-N-dodecanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. . A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 88 parts by weight of a light green powder. The heating residue of the powder in the thermogravimetric analysis was 11.8%, which almost coincided with 12.2%, which is the calculation result of N-methyl-N-dodecanoylamino nickel acetate (II) anhydride.
合成例３：Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸アルミニウム（ＩＩＩ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが３、Ｍがアルミニウムの化合物）の合成
硝酸アルミニウム（ＩＩＩ）９水和物５６重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸８６重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、白色粉末９８重量部を得た。この粉末の熱重量分析における加熱残分が４．１％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノ酢酸アルミニウム（ＩＩＩ）無水物の計算結果である４．０％とほぼ一致した。
Synthesis Example 3: N-methyl-N-dodecanoylaminoacetic acid aluminum (III) anhydride (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1, x is 3, M Is a compound of aluminum) A solution comprising 56 parts by weight of aluminum nitrate (III) nonahydrate, 86 parts by weight of N-methyl-N-dodecanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. . A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 98 parts by weight of a white powder. The heat residue of this powder in the thermogravimetric analysis was 4.1%, which almost coincided with the calculated result of N-methyl-N-dodecanoylaminoaluminum acetate (III) anhydride of 4.0%.
合成例４：Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸スズ（ＩＶ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが４、Ｍがスズの化合物）の合成
酢酸スズ（ＩＩ）３５重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸８６重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、灰色粉末６２重量部を得た。この粉末の熱重量分析における加熱残分が１２．５％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノ酢酸スズ（ＩＶ）無水物の計算結果である１２．４％とほぼ一致した。
Synthesis Example 4: N-methyl-N-dodecanoylaminoacetate tin (IV) anhydride (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1, x is 4, M A compound comprising 35 parts by weight of tin (II) acetate, 86 parts by weight of N-methyl-N-dodecanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. A solution obtained by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 62 parts by weight of a gray powder. The heating residue in the thermogravimetric analysis of this powder was 12.5%, which almost coincided with the calculated result of 1-2.4% tin (IV) anhydride of N-methyl-N-dodecanoylaminoacetate.
合成例５：Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸銀（Ｉ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが１、Ｍが銀の化合物）の合成
硝酸銀（Ｉ）２５重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸８６重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、薄黄色粉末５１重量部を得た。この粉末の熱重量分析における加熱残分が３５．２％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノ酢酸銀（Ｉ）無水物の計算結果である３５．７％とほぼ一致した。
Synthesis Example 5 N-methyl-N-dodecanoylaminoacetic acid silver (I) anhydride (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1, x is 1, M Is a silver compound) A solution comprising 25 parts by weight of silver nitrate (I), 86 parts by weight of N-methyl-N-dodecanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 51 parts by weight of a light yellow powder. The heat residue of this powder in thermogravimetric analysis was 35.2%, which almost coincided with the calculated result of silver (I) anhydride of N-methyl-N-dodecanoylaminoacetate of 35.7%.
合成例６：Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸金（ＩＩＩ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが３、Ｍが金の化合物）の合成
塩化金（ＩＩＩ）４５重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノ酢酸８６重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、黄色粉末８１重量部を得た。この粉末の熱重量分析における加熱残分が２４．４％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノ酢酸金（ＩＩＩ）無水物の計算結果である２４．４％とほぼ一致した。
Synthesis Example 6 N-methyl-N-dodecanoylaminoacetic acid gold (III) anhydride (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 1, x is 3, M A solution comprising 45 parts by weight of gold (III) chloride, 86 parts by weight of N-methyl-N-dodecanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 81 parts by weight of a yellow powder. The heating residue in thermogravimetric analysis of this powder was 24.4%, which almost coincided with the calculated result of N-methyl-N-dodecanoylaminoacetic acid gold (III) anhydride of 24.4%.
合成例７：Ｎ−メチル−Ｎ−デカノイルアミノ酢酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 9 Ｈ 19 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−デカノイルアミノ酢酸７７重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末８１重量部を得た。この粉末の熱重量分析における加熱残分が１４．６％であり、これはＮ−メチル−Ｎ−デカノイルアミノ酢酸銅（ＩＩ）無水物の計算結果である１４．５％とほぼ一致した。
Synthesis Example 7: N-methyl-N-decanoylaminoacetic acid copper (II) anhydride (R 1 in formula (1) is C 9 H 19 , R 2 is CH 3 , n is 1, x is 2, M Is a copper compound) A solution comprising 36 parts by weight of copper (II) nitrate trihydrate, 77 parts by weight of N-methyl-N-decanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. . A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 81 parts by weight of a light blue powder. This powder had a heating residue of 14.6% in thermogravimetric analysis, which almost coincided with the calculated result of N-methyl-N-decanoylamino copper acetate (II) anhydride of 14.5%.
合成例８：Ｎ−メチル−Ｎ−［（Ｚ）−１−オキソ−９−オクタデセニル］アミノ酢酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 17 Ｈ 33 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−［（Ｚ）−１−オキソ−９−オクタデセニル］アミノ酢酸１１２重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末１０１重量部を得た。この粉末の熱重量分析における加熱残分が１０．６％であり、これはＮ−メチル−Ｎ−［（Ｚ）−１−オキソ−９−オクタデセニル］アミノ酢酸銅（ＩＩ）無水物の計算結果である１０．３％とほぼ一致した。
Synthesis Example 8: N-methyl-N-[(Z) -1-oxo-9-octadecenyl] aminoacetate copper (II) anhydride (R 1 in formula (1) is C 17 H 33 , R 2 is CH 3 , a compound in which n is 1, x is 2, and M is copper ) 36 parts by weight of copper nitrate (II) trihydrate, N-methyl-N-[(Z) -1-oxo-9-octadecenyl] A solution consisting of 112 parts by weight of aminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water was prepared. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 101 parts by weight of a light blue powder. The heating residue in the thermogravimetric analysis of this powder is 10.6%, which is the calculation result of N-methyl-N-[(Z) -1-oxo-9-octadecenyl] aminoacetic acid copper (II) anhydride This is almost the same as 10.3%.
合成例９：Ｎ−メチル−Ｎ−オクタデカノイルアミノ酢酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 17 Ｈ 35 、Ｒ 2 がＣＨ 3 、ｎが１、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−オクタデカノイルアミノ酢酸１１３重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末８９重量部を得た。この粉末の熱重量分析における加熱残分が１０．４％であり、これはＮ−メチル−Ｎ−オクタデカノイルアミノ酢酸銅（ＩＩ）無水物の計算結果である１０．３％とほぼ一致した。
Synthesis Example 9: N-methyl-N-octadecanoylaminoacetic acid copper (II) anhydride (R 1 in formula (1) is C 17 H 35 , R 2 is CH 3 , n is 1, x is 2, A compound consisting of 36 parts by weight of copper nitrate (II) trihydrate, 113 parts by weight of N-methyl-N-octadecanoylaminoacetic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water. Produced. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 89 parts by weight of a light blue powder. The heating residue in the thermogravimetric analysis of this powder was 10.4%, which almost coincided with the 10.3% calculation result of N-methyl-N-octadecanoylamino copper acetate (II) anhydride. .
合成例１０：Ｎ−メチル−Ｎ−デカノイルアミノプロピオン酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 9 Ｈ 19 、Ｒ 2 がＣＨ 3 、ｎが２、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−デカノイルアミノプロピオン酸８２重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末７６重量部を得た。この粉末の熱重量分析における加熱残分が１３．９％であり、これはＮ−メチル−Ｎ−デカノイルアミノプロピオン酸銅（ＩＩ）無水物の計算結果である１３．８％とほぼ一致した。
Synthesis Example 10 N-methyl-N-decanoylaminopropionate copper (II) anhydride (R 1 in formula (1) is C 9 H 19 , R 2 is CH 3 , n is 2, x is 2, A compound comprising 36 parts by weight of copper nitrate (II) trihydrate, 82 parts by weight of N-methyl-N-decanoylaminopropionic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water. Produced. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 76 parts by weight of a light blue powder. The heat residue of this powder in the thermogravimetric analysis was 13.9%, which almost coincided with the calculated value of 13.8% for copper (II) anhydride of N-methyl-N-decanoylaminopropionate. .
合成例１１：Ｎ−メチル−Ｎ−ドデカノイルアミノプロピオン酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 11 Ｈ 23 、Ｒ 2 がＣＨ 3 、ｎが２、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−ドデカノイルアミノプロピオン酸９０重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末７５重量部を得た。この粉末の熱重量分析における加熱残分が１２．４％であり、これはＮ−メチル−Ｎ−ドデカノイルアミノプロピオン酸銅（ＩＩ）無水物の計算結果である１２．６％とほぼ一致した。
Synthesis Example 11: Copper (II) anhydride of N-methyl-N-dodecanoylaminopropionate (R 1 in formula (1) is C 11 H 23 , R 2 is CH 3 , n is 2, x is 2, A compound comprising 36 parts by weight of copper nitrate (II) trihydrate, 90 parts by weight of N-methyl-N-dodecanoylaminopropionic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water. Produced. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 75 parts by weight of a light blue powder. The heat residue of this powder in the thermogravimetric analysis was 12.4%, which almost coincided with the calculated value of 12.6% for copper (II) anhydride of N-methyl-N-dodecanoylaminopropionate. .
合成例１２：Ｎ−メチル−Ｎ−オクタデカノイルアミノプロピオン酸銅（ＩＩ）無水物（式（１）中のＲ 1 がＣ 17 Ｈ 35 、Ｒ 2 がＣＨ 3 、ｎが２、ｘが２、Ｍが銅の化合物）の合成
硝酸銅（ＩＩ）３水和物３６重量部、Ｎ−メチル−Ｎ−オクタデカノイルアミノプロピオン酸１１７重量部、エタノール７９３０重量部、及び水１００重量部からなる溶液を作製した。ここにヘキシルアミン１０重量部をエタノール６重量部に溶解した溶液を加え、１時間攪拌後、濾過・洗浄し、得られた固体を減圧乾燥することで、水色粉末９３重量部を得た。この粉末の熱重量分析における加熱残分が１０．４％であり、これはＮ−メチル−Ｎ−オクタデカノイルアミノプロピオン酸銅（ＩＩ）無水物の計算結果である９．９％とほぼ一致した。
Synthesis Example 12 N-methyl-N-octadecanoylaminopropionic acid copper (II) anhydride (R 1 in formula (1) is C 17 H 35 , R 2 is CH 3 , n is 2, x is 2 , M is a compound of copper) 36 parts by weight of copper nitrate (II) trihydrate, 117 parts by weight of N-methyl-N-octadecanoylaminopropionic acid, 7930 parts by weight of ethanol, and 100 parts by weight of water A solution was made. A solution prepared by dissolving 10 parts by weight of hexylamine in 6 parts by weight of ethanol was added thereto, stirred for 1 hour, filtered and washed, and the obtained solid was dried under reduced pressure to obtain 93 parts by weight of a light blue powder. The heating residue in the thermogravimetric analysis of this powder was 10.4%, which is almost the same as the calculated result of 9.9% of copper (II) anhydride of N-methyl-N-octadecanoylaminopropionate. did.
実施例１
平均粒径８μｍの電解銅粉末８５重量部を、フェノール樹脂（商品名「ＰＬ−５２０８」群栄化学工業株式会社製、不揮発分６０％）１５重量部、合成例１で調製したＮ−メチル−Ｎ−ドデカノイルアミノ酢酸銅（ＩＩ）無水物５．５重量部及びブチルカルビトール５重量部を、自転・公転ミキサー（機種名「ＡＲＶ−３１０」、シンキー株式会社製）及び三本ロールにて混練し、導電性組成物を作製した。得られた導電性組成物について以下の各測定を行った。各測定結果を表１に示す。
Example 1
85 parts by weight of electrolytic copper powder having an average particle size of 8 μm, 15 parts by weight of phenol resin (trade name “PL-5208” manufactured by Gunei Chemical Industry Co., Ltd., nonvolatile content 60%), N-methyl-prepared in Synthesis Example 1 N-dodecanoylaminoacetate copper (II) anhydride 5.5 parts by weight and butyl carbitol 5 parts by weight with a rotating / revolving mixer (model name “ARV-310”, manufactured by Shinkey Corporation) and a three roll It knead | mixed and produced the electroconductive composition. The following measurement was performed about the obtained electroconductive composition. Table 1 shows the measurement results.
（抵抗率の測定）
作製した導電性組成物を、ガラス基板上で縦３ｃｍ×横１ｃｍ×膜厚５０μｍの形状のパターンに成型し、１５０℃に保持した循環式恒温槽中で１５分間加熱し、焼付け硬化を行なった。得られた硬化試料について、４端子４探針法抵抗率計における測定結果とパターンの膜厚より、初期の体積抵抗率を算出した。その結果、初期の体積抵抗率は１．５×１０-3Ω・ｃｍであった。
（初期粘度及び２ヶ月経過後の粘度の測定）
作製した導電性組成物について、レオメーター（製品名「ＣＶＯ」、スペクトリス株式会社製）にて、せん断速度が５／ｓにおける粘度を測定した。その結果、初期粘度は９４Ｐａ・ｓであった。また、作製した導電性組成物を、５℃に保持した冷蔵庫において２ヶ月保管した後、せん断速度が５／ｓにおける粘度を測定した。その結果、２ヵ月後の粘度は１６６Ｐａ・ｓであった。
（印刷性）
作製した導電性組成物を用い、スクリーン印刷機（製品名「ＭＴ−３２０」、マイクロ・テック株式会社製）にてガラス基板上にパターンを作製し、１５０℃に保持した循環式恒温槽中で１５分間加熱し、焼付け硬化を行なった。得られた硬化試料の外観を目視にて以下の評価基準に従って評価した。その結果、印刷時のにじみ、かすれ等に起因する欠陥部分は見られず、評価は○であった。
印刷性の評価基準
○：欠陥無し、△：少量の欠陥あり、×：多数の欠陥あり。
(Measurement of resistivity)
The produced conductive composition was molded into a pattern having a shape of 3 cm long × 1 cm wide × 50 μm thick on a glass substrate and heated in a circulating thermostat kept at 150 ° C. for 15 minutes to be baked and cured. . With respect to the obtained cured sample, the initial volume resistivity was calculated from the measurement result of the 4-terminal 4-probe resistivity meter and the film thickness of the pattern. As a result, the initial volume resistivity was 1.5 × 10 −3 Ω · cm.
(Measurement of initial viscosity and viscosity after 2 months)
About the produced electroconductive composition, the viscosity in case the shear rate is 5 / s was measured with the rheometer (product name "CVO", the Spectris Co., Ltd. make). As a result, the initial viscosity was 94 Pa · s. Further, after the produced conductive composition was stored for 2 months in a refrigerator maintained at 5 ° C., the viscosity at a shear rate of 5 / s was measured. As a result, the viscosity after 2 months was 166 Pa · s.
(Printability)
Using the produced conductive composition, a pattern was produced on a glass substrate with a screen printing machine (product name “MT-320”, manufactured by Micro Tech Co., Ltd.), and kept in a circulating thermostat kept at 150 ° C. It was heated for 15 minutes to bake and harden. The appearance of the obtained cured sample was visually evaluated according to the following evaluation criteria. As a result, no defective portion due to bleeding or blurring during printing was observed, and the evaluation was good.
Evaluation criteria for printability ○: No defect, Δ: Small amount of defects, ×: Many defects.
実施例２〜２４及び比較例１〜９
導電性組成物の組成を表１〜５に示す組成とした以外は実施例１と同様にして導電性組成物を調製し、実施例１と同様に各測定を行なった。結果を表１〜５に示す。
Examples 2 to 24 and Comparative Examples 1 to 9
A conductive composition was prepared in the same manner as in Example 1 except that the composition of the conductive composition was changed to the compositions shown in Tables 1 to 5, and each measurement was performed in the same manner as in Example 1. The results are shown in Tables 1-5.
表１〜５から明らかなように、本発明の実施形態である実施例１〜２４の導電性組成物は、経時後の粘度及び体積抵抗率の変化が小さく保存安定性に優れ、良好な印刷特性を発揮する。 As is apparent from Tables 1 to 5, the conductive compositions of Examples 1 to 24, which are embodiments of the present invention, have small changes in viscosity and volume resistivity with time, excellent storage stability, and good printing. Demonstrate the characteristics.
Claims (4)
前記（ａ）金属粉末の元素と、前記（ｃ）式（１）で表される化合物を構成する金属Ｍの元素が同一である導電性組成物。
A conductive composition in which the element of the metal powder (a) and the element of the metal M constituting the compound represented by the formula (1) are the same.
請求項１に記載の導電性組成物。 (A) the metal powder is copper powder, (c) M of the compound represented by the formula (1) is copper, and x is 2.
The conductive composition according to claim 1.
請求項１又は２に記載の導電性組成物。 The (b) resin is a thermosetting resin.
The conductive composition according to claim 1 or 2.
請求項１〜３いずれか一項に記載の導電性組成物。 And (d) containing an amine,
The electrically conductive composition as described in any one of Claims 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013240682A JP6237150B2 (en) | 2012-11-30 | 2013-11-21 | Conductive composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012261962 | 2012-11-30 | ||
| JP2012261962 | 2012-11-30 | ||
| JP2013240682A JP6237150B2 (en) | 2012-11-30 | 2013-11-21 | Conductive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014130806A JP2014130806A (en) | 2014-07-10 |
| JP6237150B2 true JP6237150B2 (en) | 2017-11-29 |
Family
ID=51409003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013240682A Active JP6237150B2 (en) | 2012-11-30 | 2013-11-21 | Conductive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6237150B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6015736B2 (en) * | 2014-11-10 | 2016-10-26 | トヨタ自動車株式会社 | FUEL CELL SYSTEM AND CONTROL METHOD FOR FUEL CELL SYSTEM |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59167906A (en) * | 1983-03-11 | 1984-09-21 | 松下電器産業株式会社 | Conductive thick film forming composition, method for producing and using the same |
| JPH04253773A (en) * | 1991-02-05 | 1992-09-09 | Nippon Oil & Fats Co Ltd | Conductive composition |
| JP2002363473A (en) * | 2001-06-05 | 2002-12-18 | Sakura Color Prod Corp | Aqueous ink composition and aqueous ball-point pen using the same |
| JP4495644B2 (en) * | 2004-07-30 | 2010-07-07 | Ｊｆｅミネラル株式会社 | Metal super fine slurry |
| JP5521207B2 (en) * | 2009-01-28 | 2014-06-11 | 東ソー株式会社 | Conductive film forming composition, method for producing the same, and conductive film forming method |
-
2013
- 2013-11-21 JP JP2013240682A patent/JP6237150B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014130806A (en) | 2014-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6343041B2 (en) | Thermally conductive paste and use thereof | |
| JP6140189B2 (en) | Conductive paste and manufacturing method thereof | |
| CN115746625B (en) | Printing ink for screen printing | |
| JP2021138961A (en) | Thermally conductive polyorganosiloxane composition | |
| JP6118489B2 (en) | Paste-like metal particle composition, method for producing metal member assembly, and method for producing porous metal particle sintered product | |
| JP5907302B1 (en) | Copper powder, copper paste using the same, conductive paint, conductive sheet, and method for producing copper powder | |
| CN104471652B (en) | Silver-containing composition and silver component forming substrate | |
| JP2014051569A (en) | Conductive copper ink composition | |
| JP6237150B2 (en) | Conductive composition | |
| JP6884470B2 (en) | Conductive copper ink composition | |
| JP4962063B2 (en) | Conductive paste | |
| JPWO2015045932A1 (en) | Copper thin film forming composition | |
| JP5134352B2 (en) | Conductive paste | |
| JP2015067716A (en) | Thin copper film formation composition | |
| JP7147488B2 (en) | conductive composition | |
| JP2021057185A (en) | Conductive composition | |
| JP7764699B2 (en) | Manufacturing method of surface-coated copper filler | |
| JP2014086243A (en) | Paste for forming an electroconductive film, electroconductive film, method for manufacturing an electroconductive film, and article | |
| JP5293581B2 (en) | Conductive composition, method for forming conductive wiring, and conductive wiring | |
| TWI698474B (en) | Conductive composition | |
| JP5764824B2 (en) | Conductive adhesive composition and electronic device using the same | |
| JPWO2018163619A1 (en) | Method for producing silver nanoparticles | |
| JP2022036917A (en) | Conductive composition | |
| JP2023028100A (en) | conductive composition | |
| JP2020070489A (en) | Conductive fine particle dispersion, method for forming conductive pattern and method for producing conductive substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161114 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170816 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171003 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171016 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6237150 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |